CA1133179A - Additive for inorganic binders - Google Patents
Additive for inorganic bindersInfo
- Publication number
- CA1133179A CA1133179A CA329,419A CA329419A CA1133179A CA 1133179 A CA1133179 A CA 1133179A CA 329419 A CA329419 A CA 329419A CA 1133179 A CA1133179 A CA 1133179A
- Authority
- CA
- Canada
- Prior art keywords
- melamine
- urea
- water
- acid
- molar ratio
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic and acyclic or carbocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/20—Sulfonated aromatic compounds
- C04B24/22—Condensation or polymerisation products thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/34—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Abstract:
Additive for inorganic binders, such as cements, calcium sulfate, magnesia cement and the like, which com-prises, as the active ingredient, a water-soluble salt of a mixed resin consisting of an aromatic aminosulfonic acid, urea, melamine and formaldehyde, the molar ratio, in the resin, of aromatic aminosulfonic acid to the total amount of melamine and urea being (0.2 to 1.0) : 1.0 and the molar ratio of melamine to urea being from 0.75 : 0,25 to 0.30 :
0.70, and also building materials, having increased flow-ability and early strength, in which this additive is present.
Additive for inorganic binders, such as cements, calcium sulfate, magnesia cement and the like, which com-prises, as the active ingredient, a water-soluble salt of a mixed resin consisting of an aromatic aminosulfonic acid, urea, melamine and formaldehyde, the molar ratio, in the resin, of aromatic aminosulfonic acid to the total amount of melamine and urea being (0.2 to 1.0) : 1.0 and the molar ratio of melamine to urea being from 0.75 : 0,25 to 0.30 :
0.70, and also building materials, having increased flow-ability and early strength, in which this additive is present.
Description
~L~33~
Additi~e for inorganic binders The invention relates to an additive for inorganic binders ? in particular cement, which is based on'a melamine/
urea mixed resin with formaldehyde and which improves the flowability and early strength o~ the ~uilding material pro-~
: duced`therefrom9 and also to the building material produced' therewith and a process for its production It is known ~rom U.S. Patent Specification 2,141,569 that the flowability of building materials based on cement can be increased by means of agents which have a dispersing action on the cement. Since a lower water/cement~ratio ' can be maintained by increasing the flowability, it is possible to achieve higher strengths o~ the building material . , produced with this additive~ The essential constituent ; 15 of the agents used according to this U.S. patent specifica-tion consists of sulfonic acid groups which are bonded to a formaldehyde resin, these resins being obtained by the con-densation of aromatic sulfonic acids, in particular of naphthalenesulfonic acids, with formaldehyde.
Following on from the principle according to U.S.
Patent Specification 2,141,569, a number of other sulfonic acids, such as 9 for example, lignosulfonic acids (U.S0 Patent Specification 29169,980), polybenzylsulfonic acids (U.S.
: Patent Specification 2,445,569) and also resins which are - ~ 25 based on an amino-s-triazine having at least two NH2 groups and are modified by sulfite or sulfonic acid, were also proposed as dispersing agents for cements; these dispersing agents possess, in particular, a plasticizing action resulting from the possibility, associated with this'plasticizing action, of using less water, but also possess a strengthen-.ing action ' On the other hand, if the use of less mixing water ' is dispensed with, the building material becomes easier topour or pump; however', a lower early strength is exhibited, in particular in the first hours o~ the hardening stage, and this is a result o~ a delay in'the hardening processO
The modified triazine resins used according to British Patent- Speci~ication No. 1,169.582 are primarily products ~'~
resulting from the reaction of melamine/formaldeh~de resins with alkali metal sulfites or alkali metal salts of disul furous acid, in which the sulfite radical reacts with the methyloL groups of the resinO The S03H group of these modified resins is therefore primarily bonded to the tri-azine via -0-CH2- bridges, ~ In addition to these resins 9 resins modified by sulfonic acid are aiso mentioned which are derived from dia~inotriazines9 such as acetoguanamine or benzoguanamine, in which the sulfonic acid group is bonded to the methyl or phenyl group, that is to say directly to the triazine employed for forming the resinO Such sulfonic acids are very difficult to obtain and resins derived therefrom have found no use in practice Alternatively9 according to Austrian Patent Specifica~-tion 3429867, it is possible, in the production of amino-triazine/formaldehyde resins which are modified by sulfonic acid groups by being reacted with alkali metal sulfites during the formation of the resin9 to replace up to 40 mole % of the melamine by urea, wlthout affecting the action as an additive for building materials.
Surprisingly, it was possible to find that additives based on specially modified aminoplast resins9 for building materials based on inorganic binders, can be produced which have a very goodplasticizing actionwithout exerting a nega-tive influence on the development of early strength~
provided that the aminoplast resins employed are melamine/
urea/formaldehyde mixed resins which have been modified with fixed amounts of aromatic aminosulfonic acids, in particular sulfanilic acid. These new additives are distinguished in that they bring about an increase in the early strength, even when the use of less mixing water is dispensed with for the benefit of the flowability of the building material.
It is surprising, in this case, that the urea constituent in the resin is essential for achieving the good early strength, whereas, hitherto~ urea has aGted in the best case, in this respect, as an inactive substitute for the aminotria~ine.
Accordingly, the subject of the present invention~is ~33~'7 an addi-tlve for organic binders, such as, preferably, cement~
magnesia cement and calcium sulfateS which comprises a water-soluble salt of a mixed condensate of urea, melamine~
an aromatic aminosulfonic acid and formaldehyde, in which the molar ratio of the aromatic aminosulfonic acid to the total amount of melamine and ureais(O02 tol.O) : laO and the molar ratio of melamine to urea is from 0.75 : 0.25 to 0~30 :
0 70.
As a rule, the molar ratio of the total amount of melamine and urea to formaldehyde is 1 ~ 5 to 3.0)~
- Particularly favorable strength properties are achieved when the propor-tion of urea in the resin is pre-dominant relative to the melamine, that is to say the ratio of urea -to melamine is greater than 1, and it is simul~
taneously favorable to keep the proportion of formaldehyde as low as possible.
Sulfanilic acid may be mentioned in particular as the aromatic aminosulfonic acid. Other aromatic amino- .
sulfonic acids, which can be derived 9 for example, from either -20 benzene or naphthalene, are, for example, metanilic acid, . naph-thionic acid, l-naph-thylamine-6-sulfonic acid (Cleve~s acid) 9 1-naphthylamine-5-sulfonic acid (Laurent's acid), 1-;naphthylamine-3,6-disulfonic acid and 1-naphthylamine-3,6,8 trisulfonic acid.
Water-soluble salts of the modified aminoplast resins which may be mentioned are primarily the alkali metal or alkaline earth metal salts such as 9 in particular, the Na, K or Ca salt or the ammonium sal-t.
Suitable building materials to which the additive according to the invention can be added in order to improve the properties are primarily cement mortar and concrete, the additives being suitable both for pourable concrete (~eeping the amount of mixing water constan-t) and for high-strength concrete, less mixing water being used in the latter case as a resul-t of the additive according to the invention.
However, the additive according to the invention can also be successfully added to other inorganic building materials which are based on gypsum, anhydrite 9 lime, magnesia cement or alumina cement as the binder, L7~3 The additive, which as a rule is present as an approxima-tely 2~/' strength aqueous solution, is added in an amount cf 0.01 to 20~' by weight o~ solid resin in this solu-tion, relative -to the conten-t of inorganic binder in the building ma-terial. The amount is preferably 0~1 to l~/o by weigh-t of solid resin. However, the aminoplast resin produced in aqueous solu-tion can also be dried in accordance with one o~ the customary drying processes, for example the spray-drying process, i~s plasticizing properties being kept constant, and can be added to the building materials as a pulverulent resin The additive is usually admixed, immediately before processing,directlywith the mixture of the binder with water and the customary additives~ However, it is also pos-i5 sible~ for example, to mix the salt of the modified amino-plast resin initially with the mixing water and then to incor~orate the binder and the additives~such as sand, gravel and the like.
The modified aminoplast resins according to the in-vention can beproduced in accordance with customary methods.-Thus, for example, the melamine can be precondensed in the alkaline region with part of the formaldehyde and a salt, preferably an alkali metal salt of the aminosulfonic acid, and the urea, which has previously already been methylolated~
can then be added. The pH value is then lowered to values of about 4 to 6.5 by addin$ acids and the condensation is carried out until the desired viscosity, which as a rule is in the range from 5 to 50 ~Pas/20C in 2~ strength solution, is obtained, The condensation reaction is ~0 ended by increasing the pH value to values of between 7.5 and 9. However, it is also possible to precondense the melamine and urea simultaneously, to add the sulfonic acid and, after the reaction has been carried out, to initiate the actual condensation by lowering the pH valueO
The condensation is prelerably carried out at eleva-ted tempera-ture in order to shorten the reaction times.
However, it is also possible to carry out the condensation at room temperature, in particular when the reaction is carried out at low pH values.
.
~3~t7 The purpose of the following examples is -to illus-trate the present invention in greater detail~ without - intending -to restrict it theretoO
Example 1 to 12: .
a g of melamine ~M) are mixed with b g of a 36.9%
strength formaldehyde solution (F/M) in a reaction vessel and the mixture is adjusted to pH 9.0 with 3 N sodium hydroxide solution and heated; after the melamine has dis-solved, c g of the salt of the aminosulfonic acid S in d g of water (H20/S) are added. This mixture is kept at a tempera-ture of 75C for 45 minutes in the alkaline pH range (pH =
10.5) and then diluted with e gof water (H20/V)~ A solution of f g o~ urea in g g of ~6.9% strength formaldehyde solution (F/U) is then added theretoO The whole mix-ture is now acidified to pH 5J 5 to 6.o with sulfuric acid or formic acid and condensed at 75C until a viscosity of 9 ~Pas at 20C
is obtained in a Haake rotating cylinder viscometer, velocity gradient D = 976 seconds 1, is obtained. The pH value of the whole mixture is then adjusted to pH 8.5 with 30% strength sodium hydroxide solution~ After cool .~ ing to 20C, a resin solution which can be dilutPd with water and has an ef~ective solids concentration of 20 to 22~/a is obtained.
The resins thus obtained are summarized in the ~ollowing table and the aromatic aminosulfonic acid employed was as follows: sulfanilic acid in Examples ~ to 7, met-anilic acid in Example 8, 1-naphthylamin~-6-sulfonic acid in Example 9, 1-naphthylamine-4-sulfonic acid in Example 10~
l-naphthyla~ine-5-sulfonic acid in Example 11 and l-naphthyl-amine-3,C-disulfonic ac:d in Example 12.
~ .
.
~3;3~ 9 _ .
.
C~ . .
~D t~ O O O O O
~ ~o o ~ , ,-bO ~; O ~D a) ~ ÇQ O ~ C~l ~ - C`J
~ ~ I J C~ S
. .
O ~ ~ ~D C\J O O O O O O O
q~ ~ t~ ~ C`J t~ ~ t~ t~ ~D ~ ~ t~ t~
r- ~ .
u~ ~ ~ a) ~ ~ ~
. ... . . ~ . . . . .
O O~ 00 ~ ~ ~ ~D U~ t~ ~ ~ ~
C~l .~ o~ O ~ O ~ ~ ~ O O C~l t~ t-~ ~ t~ ~ t~ ~ 0 ~
. ' ~ ~ ~ D t~ O
o t~ ~ o ~ ~ ~ L~ ) t~ r~
t~l (~ LO ('.1 ~D t~ GO
1 t~\ t~l ~ Lt`~ D t~ C\l ' ,. ~ ~ ) t~ GO
~ . .. o . . ~
~ O~D O O O L~ ,~
C~
. .. L~ J ~D ~ ~ :
0 t~ ~ L~ t~ ~D O~ ~ ~ ~ O~
.,, O . O , O
L~
. , ~ . o t~ ~ Ll~ O 1~-- t~ t~ ~) ~ ~D t~ t~
. ' ~ L~ t~ ~D ~D ~ ~ ~ ~ ~D
rl ~ ~ .
L~ .
In , ~ o (U Lt~ In ~ ~
O , .. , o t ~
.,' U~ .~ ~ O ~ ~ ~ J t\i h O ~ O O O O O O O O O O
- h .. ~ ................ ~ ~o U~ ~ ~D ~ t~ 1~ 1 r~ O O O O O O O O O O O
.. LS~ .............. ~
) ~ Lt~ Lr~ 1~ LS~ . , .
. . . . . . . . O
,' . O O O O O O O O O O 'O O
. ~ .
, .~ r~l Z r~ t~ J Ll~ ~ ~ 0 ~ r-l ~ r-l :,. .
Example 13:
Pa~allel samples of a cement mor-tar were produced from PZ 275 Portland cement and, with the exception of a control sample, the additive according to the invention, produced in accordance with Example 1, was added in an amount of 1% by weight of solid resin, relative to the ~
cement. The samples were adjus-ted to a constant ~ of 15~5 to 16.0 cm and the water-sa~ing effect of the additive was thus utilized. Test pieces having dimensions of 10 4 x 4 x 16 cm were produced from -these samples in accordance with DIN 1164, hardened and tested. The results are summarized in the table, in which B is the bending tension strength and D is the compressive strength in N/cm20 i! Control Additive according - 15 to Example 1 W/C 0.53 0.4 24 hours D 1,010 1,320
Additi~e for inorganic binders The invention relates to an additive for inorganic binders ? in particular cement, which is based on'a melamine/
urea mixed resin with formaldehyde and which improves the flowability and early strength o~ the ~uilding material pro-~
: duced`therefrom9 and also to the building material produced' therewith and a process for its production It is known ~rom U.S. Patent Specification 2,141,569 that the flowability of building materials based on cement can be increased by means of agents which have a dispersing action on the cement. Since a lower water/cement~ratio ' can be maintained by increasing the flowability, it is possible to achieve higher strengths o~ the building material . , produced with this additive~ The essential constituent ; 15 of the agents used according to this U.S. patent specifica-tion consists of sulfonic acid groups which are bonded to a formaldehyde resin, these resins being obtained by the con-densation of aromatic sulfonic acids, in particular of naphthalenesulfonic acids, with formaldehyde.
Following on from the principle according to U.S.
Patent Specification 2,141,569, a number of other sulfonic acids, such as 9 for example, lignosulfonic acids (U.S0 Patent Specification 29169,980), polybenzylsulfonic acids (U.S.
: Patent Specification 2,445,569) and also resins which are - ~ 25 based on an amino-s-triazine having at least two NH2 groups and are modified by sulfite or sulfonic acid, were also proposed as dispersing agents for cements; these dispersing agents possess, in particular, a plasticizing action resulting from the possibility, associated with this'plasticizing action, of using less water, but also possess a strengthen-.ing action ' On the other hand, if the use of less mixing water ' is dispensed with, the building material becomes easier topour or pump; however', a lower early strength is exhibited, in particular in the first hours o~ the hardening stage, and this is a result o~ a delay in'the hardening processO
The modified triazine resins used according to British Patent- Speci~ication No. 1,169.582 are primarily products ~'~
resulting from the reaction of melamine/formaldeh~de resins with alkali metal sulfites or alkali metal salts of disul furous acid, in which the sulfite radical reacts with the methyloL groups of the resinO The S03H group of these modified resins is therefore primarily bonded to the tri-azine via -0-CH2- bridges, ~ In addition to these resins 9 resins modified by sulfonic acid are aiso mentioned which are derived from dia~inotriazines9 such as acetoguanamine or benzoguanamine, in which the sulfonic acid group is bonded to the methyl or phenyl group, that is to say directly to the triazine employed for forming the resinO Such sulfonic acids are very difficult to obtain and resins derived therefrom have found no use in practice Alternatively9 according to Austrian Patent Specifica~-tion 3429867, it is possible, in the production of amino-triazine/formaldehyde resins which are modified by sulfonic acid groups by being reacted with alkali metal sulfites during the formation of the resin9 to replace up to 40 mole % of the melamine by urea, wlthout affecting the action as an additive for building materials.
Surprisingly, it was possible to find that additives based on specially modified aminoplast resins9 for building materials based on inorganic binders, can be produced which have a very goodplasticizing actionwithout exerting a nega-tive influence on the development of early strength~
provided that the aminoplast resins employed are melamine/
urea/formaldehyde mixed resins which have been modified with fixed amounts of aromatic aminosulfonic acids, in particular sulfanilic acid. These new additives are distinguished in that they bring about an increase in the early strength, even when the use of less mixing water is dispensed with for the benefit of the flowability of the building material.
It is surprising, in this case, that the urea constituent in the resin is essential for achieving the good early strength, whereas, hitherto~ urea has aGted in the best case, in this respect, as an inactive substitute for the aminotria~ine.
Accordingly, the subject of the present invention~is ~33~'7 an addi-tlve for organic binders, such as, preferably, cement~
magnesia cement and calcium sulfateS which comprises a water-soluble salt of a mixed condensate of urea, melamine~
an aromatic aminosulfonic acid and formaldehyde, in which the molar ratio of the aromatic aminosulfonic acid to the total amount of melamine and ureais(O02 tol.O) : laO and the molar ratio of melamine to urea is from 0.75 : 0.25 to 0~30 :
0 70.
As a rule, the molar ratio of the total amount of melamine and urea to formaldehyde is 1 ~ 5 to 3.0)~
- Particularly favorable strength properties are achieved when the propor-tion of urea in the resin is pre-dominant relative to the melamine, that is to say the ratio of urea -to melamine is greater than 1, and it is simul~
taneously favorable to keep the proportion of formaldehyde as low as possible.
Sulfanilic acid may be mentioned in particular as the aromatic aminosulfonic acid. Other aromatic amino- .
sulfonic acids, which can be derived 9 for example, from either -20 benzene or naphthalene, are, for example, metanilic acid, . naph-thionic acid, l-naph-thylamine-6-sulfonic acid (Cleve~s acid) 9 1-naphthylamine-5-sulfonic acid (Laurent's acid), 1-;naphthylamine-3,6-disulfonic acid and 1-naphthylamine-3,6,8 trisulfonic acid.
Water-soluble salts of the modified aminoplast resins which may be mentioned are primarily the alkali metal or alkaline earth metal salts such as 9 in particular, the Na, K or Ca salt or the ammonium sal-t.
Suitable building materials to which the additive according to the invention can be added in order to improve the properties are primarily cement mortar and concrete, the additives being suitable both for pourable concrete (~eeping the amount of mixing water constan-t) and for high-strength concrete, less mixing water being used in the latter case as a resul-t of the additive according to the invention.
However, the additive according to the invention can also be successfully added to other inorganic building materials which are based on gypsum, anhydrite 9 lime, magnesia cement or alumina cement as the binder, L7~3 The additive, which as a rule is present as an approxima-tely 2~/' strength aqueous solution, is added in an amount cf 0.01 to 20~' by weight o~ solid resin in this solu-tion, relative -to the conten-t of inorganic binder in the building ma-terial. The amount is preferably 0~1 to l~/o by weigh-t of solid resin. However, the aminoplast resin produced in aqueous solu-tion can also be dried in accordance with one o~ the customary drying processes, for example the spray-drying process, i~s plasticizing properties being kept constant, and can be added to the building materials as a pulverulent resin The additive is usually admixed, immediately before processing,directlywith the mixture of the binder with water and the customary additives~ However, it is also pos-i5 sible~ for example, to mix the salt of the modified amino-plast resin initially with the mixing water and then to incor~orate the binder and the additives~such as sand, gravel and the like.
The modified aminoplast resins according to the in-vention can beproduced in accordance with customary methods.-Thus, for example, the melamine can be precondensed in the alkaline region with part of the formaldehyde and a salt, preferably an alkali metal salt of the aminosulfonic acid, and the urea, which has previously already been methylolated~
can then be added. The pH value is then lowered to values of about 4 to 6.5 by addin$ acids and the condensation is carried out until the desired viscosity, which as a rule is in the range from 5 to 50 ~Pas/20C in 2~ strength solution, is obtained, The condensation reaction is ~0 ended by increasing the pH value to values of between 7.5 and 9. However, it is also possible to precondense the melamine and urea simultaneously, to add the sulfonic acid and, after the reaction has been carried out, to initiate the actual condensation by lowering the pH valueO
The condensation is prelerably carried out at eleva-ted tempera-ture in order to shorten the reaction times.
However, it is also possible to carry out the condensation at room temperature, in particular when the reaction is carried out at low pH values.
.
~3~t7 The purpose of the following examples is -to illus-trate the present invention in greater detail~ without - intending -to restrict it theretoO
Example 1 to 12: .
a g of melamine ~M) are mixed with b g of a 36.9%
strength formaldehyde solution (F/M) in a reaction vessel and the mixture is adjusted to pH 9.0 with 3 N sodium hydroxide solution and heated; after the melamine has dis-solved, c g of the salt of the aminosulfonic acid S in d g of water (H20/S) are added. This mixture is kept at a tempera-ture of 75C for 45 minutes in the alkaline pH range (pH =
10.5) and then diluted with e gof water (H20/V)~ A solution of f g o~ urea in g g of ~6.9% strength formaldehyde solution (F/U) is then added theretoO The whole mix-ture is now acidified to pH 5J 5 to 6.o with sulfuric acid or formic acid and condensed at 75C until a viscosity of 9 ~Pas at 20C
is obtained in a Haake rotating cylinder viscometer, velocity gradient D = 976 seconds 1, is obtained. The pH value of the whole mixture is then adjusted to pH 8.5 with 30% strength sodium hydroxide solution~ After cool .~ ing to 20C, a resin solution which can be dilutPd with water and has an ef~ective solids concentration of 20 to 22~/a is obtained.
The resins thus obtained are summarized in the ~ollowing table and the aromatic aminosulfonic acid employed was as follows: sulfanilic acid in Examples ~ to 7, met-anilic acid in Example 8, 1-naphthylamin~-6-sulfonic acid in Example 9, 1-naphthylamine-4-sulfonic acid in Example 10~
l-naphthyla~ine-5-sulfonic acid in Example 11 and l-naphthyl-amine-3,C-disulfonic ac:d in Example 12.
~ .
.
~3;3~ 9 _ .
.
C~ . .
~D t~ O O O O O
~ ~o o ~ , ,-bO ~; O ~D a) ~ ÇQ O ~ C~l ~ - C`J
~ ~ I J C~ S
. .
O ~ ~ ~D C\J O O O O O O O
q~ ~ t~ ~ C`J t~ ~ t~ t~ ~D ~ ~ t~ t~
r- ~ .
u~ ~ ~ a) ~ ~ ~
. ... . . ~ . . . . .
O O~ 00 ~ ~ ~ ~D U~ t~ ~ ~ ~
C~l .~ o~ O ~ O ~ ~ ~ O O C~l t~ t-~ ~ t~ ~ t~ ~ 0 ~
. ' ~ ~ ~ D t~ O
o t~ ~ o ~ ~ ~ L~ ) t~ r~
t~l (~ LO ('.1 ~D t~ GO
1 t~\ t~l ~ Lt`~ D t~ C\l ' ,. ~ ~ ) t~ GO
~ . .. o . . ~
~ O~D O O O L~ ,~
C~
. .. L~ J ~D ~ ~ :
0 t~ ~ L~ t~ ~D O~ ~ ~ ~ O~
.,, O . O , O
L~
. , ~ . o t~ ~ Ll~ O 1~-- t~ t~ ~) ~ ~D t~ t~
. ' ~ L~ t~ ~D ~D ~ ~ ~ ~ ~D
rl ~ ~ .
L~ .
In , ~ o (U Lt~ In ~ ~
O , .. , o t ~
.,' U~ .~ ~ O ~ ~ ~ J t\i h O ~ O O O O O O O O O O
- h .. ~ ................ ~ ~o U~ ~ ~D ~ t~ 1~ 1 r~ O O O O O O O O O O O
.. LS~ .............. ~
) ~ Lt~ Lr~ 1~ LS~ . , .
. . . . . . . . O
,' . O O O O O O O O O O 'O O
. ~ .
, .~ r~l Z r~ t~ J Ll~ ~ ~ 0 ~ r-l ~ r-l :,. .
Example 13:
Pa~allel samples of a cement mor-tar were produced from PZ 275 Portland cement and, with the exception of a control sample, the additive according to the invention, produced in accordance with Example 1, was added in an amount of 1% by weight of solid resin, relative to the ~
cement. The samples were adjus-ted to a constant ~ of 15~5 to 16.0 cm and the water-sa~ing effect of the additive was thus utilized. Test pieces having dimensions of 10 4 x 4 x 16 cm were produced from -these samples in accordance with DIN 1164, hardened and tested. The results are summarized in the table, in which B is the bending tension strength and D is the compressive strength in N/cm20 i! Control Additive according - 15 to Example 1 W/C 0.53 0.4 24 hours D 1,010 1,320
2 dc~_ D 1,980 2,510 4 days 25 D ~,210 ~3,540 7 days ~ 618 670 D 3,690 4;,430 Example 14:
Samples having a constant water/cement ratio of 0.5 were also produced with PZ 275 Portland cement and, with the exception of the control experiment~ the additives according to Examples 1 to 12 were used as in Example 13 The test was carried out in accordance with DIN 1164, test pieces having overall dimensions o~ 4 x 4 x 16 cm being produced. The results are recorded in the table~ ~ and D again being the bending tension strength and compressiYe strength in N/cm2.
~133~ 1~9 -s' S ,~ ~ 8 Example 8~e~ cm 9 18 hours 24 hours , DIN 1164 B D B D
Control 12~3 278 1,190 360 1,640 1 ~2,8 ~141,'350 420 1,'810 2 25,2 ~531,'350 467 1,`850
Samples having a constant water/cement ratio of 0.5 were also produced with PZ 275 Portland cement and, with the exception of the control experiment~ the additives according to Examples 1 to 12 were used as in Example 13 The test was carried out in accordance with DIN 1164, test pieces having overall dimensions o~ 4 x 4 x 16 cm being produced. The results are recorded in the table~ ~ and D again being the bending tension strength and compressiYe strength in N/cm2.
~133~ 1~9 -s' S ,~ ~ 8 Example 8~e~ cm 9 18 hours 24 hours , DIN 1164 B D B D
Control 12~3 278 1,190 360 1,640 1 ~2,8 ~141,'350 420 1,'810 2 25,2 ~531,'350 467 1,`850
3 25.~ 3291,'240 4C7 17'810 ,
4 24.0 3351,'~30 456 1,770 2~,0 3101,'210 424 1~`700 6 25.2 3201~'170 425 1,'5gO
' 10 7 23~8 31619'337 350 1,'660 8 23.0 3101,'200 ~00 1,'820 g 22,4 3501,'320. 365 1,'620 ' 10 22,2 354 1,290 476 1,824 11 20.6 375 1~200 350 1,580 15 12 18.0 3691,`150 3~5 1,'470 ' Example 15:
A concrete mix was produced in a compulsory type ` mixer from 8.3 kg of PZ 275 Portland cement 3 4.98 kg of water'~ 10.88 kg of gravel of O - 1 mm round grain9 10.88 kg of , 20' gravel of 1 - 4 mm round grain, 8.16 kg of grave~ of 4 - 8'mm ; . , round grain, 13.6 kg of gravel of 8 - 16 mrn round grain a~d , 10.88 kg of gravel of 16 - 32 mm round grain. The ~ of :, . the reference concrete~ determined in accordance with AUSTRIAN
:~ . STANDARD SPECIFICATION 3~303, was 40 cm.
If the aqueous resin solution produced in accordance ,with Example 1 is added to the concrete~ at the same W/C
ratio, in an amount corresponding to 0.4% of solid resin, relative to the cement, the s ~ ~increases to 53 cm.
~ The development of compressive strength of the pour-,~ 30 able concrete produced according to,the invention has the ~ollowing values, in N/cm 9, which are given in comparison ' with the control.
~33~
o g Resin according Control to Example 1 12 hours 203 77 18 hou~s 550 360 48 hours 1~820 1,540 7 days 2,770 2,470 28 days 3,720 3,3~0 Example 16:
- Using the same additives as described in Example 15 ~.3 kg of PZ 275 Portland cement were processçd to give a ~ concrete (~/C = 0.58) which possessed a ~ ol 40 cm -Ç according to AUSTRIAN STAND~RD SPECIFICATION 3,30~. If the resin solution according to Example 1 is added, when preparing the same concrete mix, in an amount corresponding to o,6% of solid resin, relative to the cement, a W/C ratio of only 0 54 is required in order to achieve approximately the same ~ of 40.5 cm.
The concrete thus obtained possessed a compressive strength of 2,700 N/cm2 after 2 days, ~,090 N/cm~ after 4 days, 3,410 N/cm2 after 7 days and 4,330 N/cm2 after 28 days, in contrast to the control e~periment which gave a com-pressive strength of 1,900 N/cm2 after 2 days, 2,250 N/cm2 after 4 days~ 2,750 N/cm2 after 7 days and 3,930 N/cm2 after 28 days.
Example 17:
1,200 g OI stucco plaster and 504 g of water were intimately mixed in a compulsory type mi~er in accordance with DIN 1164, sheet 7, and the s ~ was determined as 19 cm, Mixtures containing the same amount of plaster were now prepared, with the addition of the aqueous resin solu-tion according to Example 1 in an amount corresponding to an addition of 0.5% of solid resin, relative to the plaster, and the amount of wate~ was reduced, compared with the con-trol, until the ~ was adjusted to 19 cm.
Test pieces having overall dimensions of 4 x 4 x 16 cm were produced from all 3 samples ~ After strippingj the plaster prisms thus obtained were stored 33~79!
for 7 days under standard climatic conditions ( 65% atmos-pheric humidity~ 22C) andthen dried to constant weight at40C.
The values for the bending tension strength and compressive strength, in Nlcm2, determined in accordance with DIN 11645 are given in the following table, Bending Compressive tension strength strength Control 540 2,610 Resin according781 3 260 10 to Example 1 Example 18:
A ma~nesia cement was produced from 226.8 g of MgC12.6H20, 600 g of calcined magnesite, 21203 g OI wa-ter, - 200 g of matchwood and 60 6 g of the resin solution accord-ing to Example 1~ corresponding to 2% of solid resin, As a control, -the same amounts of MgC12.6H20, magnesite and matchwood were only mixed with an amount of water of 272.8 g, with no resin content. Both mixtures were filled into 4 x 4 x 16 cm molds, dried for 1 hour at 120C and stored for 10 days at 23C~ The tests of the bending tension strength and -the compressive strength gave 815 N/cm2 and 1,630 N/cm2, respectively, in the case of the magnesia ` cemen-t according to the inventionl compared with 565 N/cm and 1,150 N/cm in the case of the contr~10 Example 19:
192.8 g of 35% strength formaldehyde solution are placed in a reaction flask and 50.4 g of melamine and 36 g o~ urea are introduced, whilst stirring. The heating is now switched on and, at 25C, the pH value of the mixture is adjusted to pH 9 0 with sodium hydroxide solution. The temperature is raised to 80C in the course of 15 mi~utes.
At this temperature, a clear solution is formed. The Na sulfanilate solution prepared as follows is then added:
271.2 g of distilled H20 and 16 g of caustic soda are treated, after dissolution of the caustic soda, with 69,2 g of sulfanilic acid and, if necessary, the pH is adjusted to 10.5 with 5~/0 s-treng-th NaOH solution~
The pH value of *he whole mixture is adjusted to 10.5 by means of sodium hydroxide solution and the mixture is allowed to react for 45 minutes at 75C. ~It is then , ~33~7~ ~
. .
diluted with 401~7 g of distilled H20 and the reaction mix-ture is cooled to 55C . The pH value is adjusted to 5 . O
with 20% strength formic acidO A-t 55C ~ the mixture is condensed until a viscosi-ty of 63 to 67 seconds, at 20C in a 2 mm DIN flow cup 9 iS obtained, After the desired vis-cosity has been reached, the pH value of the whole mixture is adjusted to 8~ 5 with 50YO strength NaOH solution a~d cooled to room temperature in the course of 30 minu-tes, Properties of the resin:
10 Viscosity 8 - 10 ~Pas - Solids content about 2~/o Properties of a cement mortar according to DIN 1164, containing PZ 275 cement, after 18 hours Water/cement ratio 0~5 1% of solid resin/cement Resin composition U / M / S / F = o.6 ~ 0-41 o.4 / 2.25 2 &~ N/mm in cm ~ B/B D D/Do _ _ 20 Reference sample 13~8 3.15 13.5 Resin 20 - 21 3052 1,12 14,0 1,04 _ , , , , _ . . _ .
Example 20:
Resins having the composition given below, which were produced analogously to Examples 1 - 12 and 19, were processed with 2 samples of PZ 275 cemen~ of different origin to gi~e a cement mortar according to DIN 1164 and were tested, The water/cement ratio was 0.5 and the addition of resin amounted to 1% of solid resin, relati~e to the cement~ The test was carried out 18 hours after the preparation of the mortar, The composition of the resins was chosen so that a constant ratio of formaldehyde to urea o~ 1,0 and a constant ratio of formaldehyde to melamine of 2,5 was maintained, The resins were employed as an approximately 2~/o strength aqueous solution. The~ results are summarized in the table in which A ls the ~ ~ In order to illustrate the effect more clearly, the ratio of the compressive strength or bending tension strength achieved to the values for the cement mortar sample without ~33~L7 -- 12 ~
added resin is also given in the table, Cement 1 Resin A B 2 BjBo ¦ D D/Do U M : F : S cm N/mm _ _ N/mm , _ ____ wi-thout resin 13.65 3,04 14012 0,2:0.8:0~4:2,20 26,8 2.65 0.87 ll.L~ 0.81 0,3:0.7:0.4~2,05 27,0 2,62 0,86 12,46 0,88 o.4:o.6:0,4:1.9 not determil led 0.5:0,5:0~4:1.75 25.1 3,11 1.02 12,~6 0,88 0 6~ 25.23.27 1.08 13.14 0,93 Cement 2 Resin AB 2 ~/Bo D 2 D/Do U : M : F o S cmN/mm N/mm , , _ _ _ . ~ ~ __~
without resin 1~.4 2,03 7.79 15 0,2:0.8:0.4 2,20 24,0 1.74 0,86 7.27 0.9~
` 0,3:0.7:0.4:2,05 23.7 2.17 1,07 8061 1,11 ;~ ' 0.4:0.6:0,4:1,9 23,9 2.25 1.11 8,86 1.14 0,5:0,5:0,4:1,75 23,2 2,21 1,07 8.66 1.11 0,6:0.4:0.4:1.6 23.0 3.12 1.54 10.2 1.3 .
~ . .. .
.
~,i , ,, , ' .
` , -.
' ~ .
: ,:
' 10 7 23~8 31619'337 350 1,'660 8 23.0 3101,'200 ~00 1,'820 g 22,4 3501,'320. 365 1,'620 ' 10 22,2 354 1,290 476 1,824 11 20.6 375 1~200 350 1,580 15 12 18.0 3691,`150 3~5 1,'470 ' Example 15:
A concrete mix was produced in a compulsory type ` mixer from 8.3 kg of PZ 275 Portland cement 3 4.98 kg of water'~ 10.88 kg of gravel of O - 1 mm round grain9 10.88 kg of , 20' gravel of 1 - 4 mm round grain, 8.16 kg of grave~ of 4 - 8'mm ; . , round grain, 13.6 kg of gravel of 8 - 16 mrn round grain a~d , 10.88 kg of gravel of 16 - 32 mm round grain. The ~ of :, . the reference concrete~ determined in accordance with AUSTRIAN
:~ . STANDARD SPECIFICATION 3~303, was 40 cm.
If the aqueous resin solution produced in accordance ,with Example 1 is added to the concrete~ at the same W/C
ratio, in an amount corresponding to 0.4% of solid resin, relative to the cement, the s ~ ~increases to 53 cm.
~ The development of compressive strength of the pour-,~ 30 able concrete produced according to,the invention has the ~ollowing values, in N/cm 9, which are given in comparison ' with the control.
~33~
o g Resin according Control to Example 1 12 hours 203 77 18 hou~s 550 360 48 hours 1~820 1,540 7 days 2,770 2,470 28 days 3,720 3,3~0 Example 16:
- Using the same additives as described in Example 15 ~.3 kg of PZ 275 Portland cement were processçd to give a ~ concrete (~/C = 0.58) which possessed a ~ ol 40 cm -Ç according to AUSTRIAN STAND~RD SPECIFICATION 3,30~. If the resin solution according to Example 1 is added, when preparing the same concrete mix, in an amount corresponding to o,6% of solid resin, relative to the cement, a W/C ratio of only 0 54 is required in order to achieve approximately the same ~ of 40.5 cm.
The concrete thus obtained possessed a compressive strength of 2,700 N/cm2 after 2 days, ~,090 N/cm~ after 4 days, 3,410 N/cm2 after 7 days and 4,330 N/cm2 after 28 days, in contrast to the control e~periment which gave a com-pressive strength of 1,900 N/cm2 after 2 days, 2,250 N/cm2 after 4 days~ 2,750 N/cm2 after 7 days and 3,930 N/cm2 after 28 days.
Example 17:
1,200 g OI stucco plaster and 504 g of water were intimately mixed in a compulsory type mi~er in accordance with DIN 1164, sheet 7, and the s ~ was determined as 19 cm, Mixtures containing the same amount of plaster were now prepared, with the addition of the aqueous resin solu-tion according to Example 1 in an amount corresponding to an addition of 0.5% of solid resin, relative to the plaster, and the amount of wate~ was reduced, compared with the con-trol, until the ~ was adjusted to 19 cm.
Test pieces having overall dimensions of 4 x 4 x 16 cm were produced from all 3 samples ~ After strippingj the plaster prisms thus obtained were stored 33~79!
for 7 days under standard climatic conditions ( 65% atmos-pheric humidity~ 22C) andthen dried to constant weight at40C.
The values for the bending tension strength and compressive strength, in Nlcm2, determined in accordance with DIN 11645 are given in the following table, Bending Compressive tension strength strength Control 540 2,610 Resin according781 3 260 10 to Example 1 Example 18:
A ma~nesia cement was produced from 226.8 g of MgC12.6H20, 600 g of calcined magnesite, 21203 g OI wa-ter, - 200 g of matchwood and 60 6 g of the resin solution accord-ing to Example 1~ corresponding to 2% of solid resin, As a control, -the same amounts of MgC12.6H20, magnesite and matchwood were only mixed with an amount of water of 272.8 g, with no resin content. Both mixtures were filled into 4 x 4 x 16 cm molds, dried for 1 hour at 120C and stored for 10 days at 23C~ The tests of the bending tension strength and -the compressive strength gave 815 N/cm2 and 1,630 N/cm2, respectively, in the case of the magnesia ` cemen-t according to the inventionl compared with 565 N/cm and 1,150 N/cm in the case of the contr~10 Example 19:
192.8 g of 35% strength formaldehyde solution are placed in a reaction flask and 50.4 g of melamine and 36 g o~ urea are introduced, whilst stirring. The heating is now switched on and, at 25C, the pH value of the mixture is adjusted to pH 9 0 with sodium hydroxide solution. The temperature is raised to 80C in the course of 15 mi~utes.
At this temperature, a clear solution is formed. The Na sulfanilate solution prepared as follows is then added:
271.2 g of distilled H20 and 16 g of caustic soda are treated, after dissolution of the caustic soda, with 69,2 g of sulfanilic acid and, if necessary, the pH is adjusted to 10.5 with 5~/0 s-treng-th NaOH solution~
The pH value of *he whole mixture is adjusted to 10.5 by means of sodium hydroxide solution and the mixture is allowed to react for 45 minutes at 75C. ~It is then , ~33~7~ ~
. .
diluted with 401~7 g of distilled H20 and the reaction mix-ture is cooled to 55C . The pH value is adjusted to 5 . O
with 20% strength formic acidO A-t 55C ~ the mixture is condensed until a viscosi-ty of 63 to 67 seconds, at 20C in a 2 mm DIN flow cup 9 iS obtained, After the desired vis-cosity has been reached, the pH value of the whole mixture is adjusted to 8~ 5 with 50YO strength NaOH solution a~d cooled to room temperature in the course of 30 minu-tes, Properties of the resin:
10 Viscosity 8 - 10 ~Pas - Solids content about 2~/o Properties of a cement mortar according to DIN 1164, containing PZ 275 cement, after 18 hours Water/cement ratio 0~5 1% of solid resin/cement Resin composition U / M / S / F = o.6 ~ 0-41 o.4 / 2.25 2 &~ N/mm in cm ~ B/B D D/Do _ _ 20 Reference sample 13~8 3.15 13.5 Resin 20 - 21 3052 1,12 14,0 1,04 _ , , , , _ . . _ .
Example 20:
Resins having the composition given below, which were produced analogously to Examples 1 - 12 and 19, were processed with 2 samples of PZ 275 cemen~ of different origin to gi~e a cement mortar according to DIN 1164 and were tested, The water/cement ratio was 0.5 and the addition of resin amounted to 1% of solid resin, relati~e to the cement~ The test was carried out 18 hours after the preparation of the mortar, The composition of the resins was chosen so that a constant ratio of formaldehyde to urea o~ 1,0 and a constant ratio of formaldehyde to melamine of 2,5 was maintained, The resins were employed as an approximately 2~/o strength aqueous solution. The~ results are summarized in the table in which A ls the ~ ~ In order to illustrate the effect more clearly, the ratio of the compressive strength or bending tension strength achieved to the values for the cement mortar sample without ~33~L7 -- 12 ~
added resin is also given in the table, Cement 1 Resin A B 2 BjBo ¦ D D/Do U M : F : S cm N/mm _ _ N/mm , _ ____ wi-thout resin 13.65 3,04 14012 0,2:0.8:0~4:2,20 26,8 2.65 0.87 ll.L~ 0.81 0,3:0.7:0.4~2,05 27,0 2,62 0,86 12,46 0,88 o.4:o.6:0,4:1.9 not determil led 0.5:0,5:0~4:1.75 25.1 3,11 1.02 12,~6 0,88 0 6~ 25.23.27 1.08 13.14 0,93 Cement 2 Resin AB 2 ~/Bo D 2 D/Do U : M : F o S cmN/mm N/mm , , _ _ _ . ~ ~ __~
without resin 1~.4 2,03 7.79 15 0,2:0.8:0.4 2,20 24,0 1.74 0,86 7.27 0.9~
` 0,3:0.7:0.4:2,05 23.7 2.17 1,07 8061 1,11 ;~ ' 0.4:0.6:0,4:1,9 23,9 2.25 1.11 8,86 1.14 0,5:0,5:0,4:1,75 23,2 2,21 1,07 8.66 1.11 0,6:0.4:0.4:1.6 23.0 3.12 1.54 10.2 1.3 .
~ . .. .
.
~,i , ,, , ' .
` , -.
' ~ .
: ,:
Claims (10)
1. Additive for inorganic binders, such as, preferably, cement, magnesia cement and calcium sulfate, which comprises a water-soluble salt of a mixed condensate of urea, melamine, an aromatic aminosulfonic acid and formaldehyde, in which the molar ratio of the aromatic aminosulfonic acid to the total amount of melamine and urea is (0.2 to 1.0) : 1.0 and the molar ratio of melamine to urea is from 0,75 : 0.25 to 0.30 : 0.70.
2. Additive according to claim 1, in which the molar ratio of urea and melamine, together, to formaldehyde, in the water-soluble salt of the mixed condensate, is 1 : (1.5 to 3.0).
3. Additive according to claim 1, in which the aromatic aminosulfonic acid is chosen from the group consisting of sulfanilic acid, metanilic acid, naphthyl-1-amine-6-sulfonic acid and naphthyl-1-amine-4-sulfonic acid.
4. Additive according to claim 1, in which the water-soluble salt of the mixed condensate is an alkali metal salt, alkaline earth metal salt or ammonium salt.
5. Additive according to claim 1, in which the molar ratio of urea to melamine in the water soluble salt of the mixed condensate is greater than 1.
6. A mixture containing an inorganic binder from the group consisting of cement, magnesia cement and calcium sulfate, and having improved flowability and increased early strength, which comprises water,the inorganic binder and 0.01 to 20%, relative to the inorganic binder, of a water-soluble salt of a mixed condensate of urea, melamine, an aromatic aminosulfonic acid and formaldehyde, in which the molar ratio of the aromatic aminosulfonic acid to the total amount of urea and melamine is from 0.2 to 1.0 : 1 and the molar ratio of melamine to urea is from 0.75 : 0.25 to 0.30 : 0.70.
7, Mixture containing an inorganic binder, according to claim 6, in which the molar ratio of urea and melamine, together, to formaldehyde, in the water-soluble salt of the mixed condensate, is 1 : (1.5 to 3.0).
Mixture containing an inorganic binder, according to claim 6, in which the aromatic aminosulfonic acid is chosen from the group consisting of sulfanilic acid, metanilic aeid, naphthyl-1-amine-6-sulfonic acid and naphthyl-1-amine-4-sulfonic acid.
9. Mixture containing an inorganic binder, according to claim 6, in which the, water-soluble salt of the mixed con-densate is an alkali metal salt, alkaline earth metal salt or ammonium salt.
10. Mixture containing an inorganic binder, according to claim 6, in which the molar ratio of urea to melamine in the water-soluble salt of the mixed condensate is greater than 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT336778A AT357547B (en) | 1978-05-05 | 1978-05-10 | METHOD FOR PRODUCING 3-PHENYL-PYRIDAZONE- (6) |
| DE19782826447 DE2826447A1 (en) | 1978-05-10 | 1978-06-16 | ADDITIVES FOR INORGANIC BINDERS |
| DEP2826447.3 | 1978-06-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1133179A true CA1133179A (en) | 1982-10-05 |
Family
ID=25599938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA329,419A Expired CA1133179A (en) | 1978-05-10 | 1979-06-07 | Additive for inorganic binders |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4272430A (en) |
| EP (1) | EP0006135B1 (en) |
| JP (1) | JPS5919901B2 (en) |
| CA (1) | CA1133179A (en) |
| DD (2) | DD144255A1 (en) |
| DE (1) | DE2826447A1 (en) |
| DK (1) | DK218779A (en) |
| FI (1) | FI791633A (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3107852A1 (en) * | 1981-03-02 | 1982-09-16 | Sika AG, vorm. Kaspar Winkler & Co., 8048 Zürich | METHOD FOR PRODUCING HIGH CONCENTRATED, LOW VISCOSES, AQUEOUS SOLUTIONS OF MELAMINE / ALDEHYDE RESIN |
| CH648570A5 (en) * | 1981-10-26 | 1985-03-29 | Sika Ag | POLYCONDENSATION PRODUCT. |
| JPS58151354A (en) * | 1982-03-03 | 1983-09-08 | 日本ゼオン株式会社 | Cement water-reducing admixture and cement dispersion thereby |
| EP0099954B1 (en) * | 1982-07-28 | 1986-10-22 | CHRYSO SA - Ets. de TOULOUSE | Liquefactants for hydraulic binders |
| US4677159A (en) * | 1985-10-16 | 1987-06-30 | Kuwait Institute For Scientific Research | Process for the synthesis of highly stable sulfonated melamine-formaldehyde condensates as superplasticizing admixtures in concrete |
| EP0248098A1 (en) * | 1986-06-05 | 1987-12-09 | Kuwait Institute For Scientific Research | Utilization of melamine waste effluent |
| US5256199A (en) * | 1990-08-03 | 1993-10-26 | Kao Corporation | Cement admixture |
| US5424390A (en) * | 1993-05-17 | 1995-06-13 | Handy Chemicals Limited | Processes for manufacture of sulfonated melamine-formaldehyde resins |
| AT400147B (en) * | 1993-09-30 | 1995-10-25 | Chemie Linz Gmbh | MODIFIED MELAMINE RESINS, THEIR PRODUCTION AND USE, METHOD FOR IMPROVING THE FLUID AND HARDENING PROPERTIES OF INORGANIC BINDING AGENTS, BINDING AGENT MIXTURE AND BUILDING MATERIAL |
| DE4430362A1 (en) * | 1994-08-26 | 1996-02-29 | Sueddeutsche Kalkstickstoff | Flow improver for cement-contg. binder suspensions |
| US6214965B1 (en) | 1998-10-23 | 2001-04-10 | Nissan Chemical Industries, Ltd. | Process for preparing an aqueous solution of sulfanilic acid modified melamine-formaldehyde resin and a cement composition |
| US11230497B2 (en) | 2019-04-10 | 2022-01-25 | Saudi Arabian Oil Company | Cement additives |
| US10836950B1 (en) | 2019-04-29 | 2020-11-17 | Saudi Arabian Oil Company | Method for improving cement toughness |
| CN115611554B (en) * | 2021-03-02 | 2023-12-22 | 北京研筑久筑建筑科技有限公司 | Modified epoxy resin anti-abrasion repair mortar and preparation method thereof |
| US12071589B2 (en) | 2021-10-07 | 2024-08-27 | Saudi Arabian Oil Company | Water-soluble graphene oxide nanosheet assisted high temperature fracturing fluid |
| US11858039B2 (en) | 2022-01-13 | 2024-01-02 | Saudi Arabian Oil Company | Direct ink printing of multi-material composite structures |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE342867C (en) * | ||||
| US2141569A (en) * | 1932-11-21 | 1938-12-27 | Dewey And Almy Chem Comp | Concrete and hydraulic cement |
| US2169980A (en) * | 1934-11-06 | 1939-08-15 | Master Builders Co | Cement mix |
| US2445569A (en) * | 1944-07-17 | 1948-07-20 | Du Pont | Sulfonated polybenzyl |
| GB628818A (en) | 1945-08-25 | 1949-09-06 | American Cyanamid Co | Improvements in or relating to the production of water-soluble methylol melamine condensation products |
| US2407599A (en) * | 1946-03-23 | 1946-09-10 | Resinous Prod & Chemical Co | Resinous compositions and process of making same |
| US2809954A (en) * | 1954-01-26 | 1957-10-15 | Switzer Brothers Inc | Thermoplastic melamine-sulfonamideformaldehyde resinous materials and process for making same |
| DE1671017C3 (en) | 1966-02-11 | 1978-10-05 | Sueddeutsche Kalkstickstoff-Werke Ag, 8223 Trostberg | Inorganic-organic building material |
| DE1908094C3 (en) * | 1969-02-19 | 1978-11-09 | Basf -, 6700 Ludwigshafen | Use of aqueous solutions of aminoplast resin condensates as potion resin solutions |
| US3899468A (en) * | 1972-09-25 | 1975-08-12 | Cities Service Co | Novel interpolymer of amine, aldehyde and sulfanilamide |
| DE2359291C2 (en) * | 1973-11-28 | 1975-06-12 | Sueddeutsche Kalkstickstoff-Werke Ag, 8223 Trostberg | Process for the preparation of anionic melamine-formaldehyde condensation products containing sulfonic acid groups in aqueous solution with a high solids content |
| DE2505578C3 (en) * | 1974-09-23 | 1979-05-23 | Skw Trostberg Ag, 8223 Trostberg | Process for the preparation of anionic melamine-urea-formaldehyde condensation products containing sulphonic acid groups in aqueous solution with a high solids content |
| US4125410A (en) * | 1975-08-27 | 1978-11-14 | Nippon Zeon Co., Ltd. | Water-reducing admixture |
| JPS53126030A (en) * | 1977-04-11 | 1978-11-02 | Nisso Master Builders Kk | Cement composition |
-
1978
- 1978-06-16 DE DE19782826447 patent/DE2826447A1/en not_active Withdrawn
-
1979
- 1979-05-15 EP EP79101486A patent/EP0006135B1/en not_active Expired
- 1979-05-23 FI FI791633A patent/FI791633A/en not_active Application Discontinuation
- 1979-05-28 DK DK218779A patent/DK218779A/en not_active Application Discontinuation
- 1979-06-07 CA CA329,419A patent/CA1133179A/en not_active Expired
- 1979-06-08 US US06/046,778 patent/US4272430A/en not_active Expired - Lifetime
- 1979-06-14 DD DD79213625A patent/DD144255A1/en unknown
- 1979-06-14 DD DD79218543A patent/DD148759A1/en unknown
- 1979-06-16 JP JP54075189A patent/JPS5919901B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| US4272430A (en) | 1981-06-09 |
| DE2826447A1 (en) | 1980-01-03 |
| DD148759A1 (en) | 1981-06-10 |
| JPS557590A (en) | 1980-01-19 |
| DD144255A1 (en) | 1980-10-08 |
| DK218779A (en) | 1979-12-17 |
| FI791633A (en) | 1979-12-17 |
| EP0006135B1 (en) | 1981-09-16 |
| EP0006135A1 (en) | 1980-01-09 |
| JPS5919901B2 (en) | 1984-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1133179A (en) | Additive for inorganic binders | |
| US4725665A (en) | Use of salts of water-soluble | |
| FI78894B (en) | DISPERGERINGSMEDEL FOER SALTHALTIGA SYSTEM. | |
| US2141569A (en) | Concrete and hydraulic cement | |
| DK172718B1 (en) | Process for Preparation of High Concentrated, Low Viscous Aqueous Solutions of Melamine / Aldehyde Resins | |
| US4125410A (en) | Water-reducing admixture | |
| US3997502A (en) | Mortar of inorganic binder and formaldehyde condensation product of sulfonated aromatic ether, imine or sulfone | |
| US4655838A (en) | Cement additive composition | |
| US3954677A (en) | Sulfonated aromatic-formaldehyde condensation products | |
| US4079040A (en) | Sulfo-containing phenol-formaldehyde condensates | |
| JP2505397B2 (en) | Method for producing fluidizing agent for hydraulic binder | |
| US5101007A (en) | Process for the preparation of naphthalenesulfonic acid/formaldehyde condensates having a low free formaldehyde content | |
| AU578925B2 (en) | Water reducing additive for mortar and concrete | |
| CZ83993A3 (en) | The use of melamine and glyoxylic acid condensation products as an ingredient in hydraulic binding agents | |
| JPH01129016A (en) | Production of fluidizing agent for inorganic binder | |
| US4414034A (en) | Novel additive blends for cementitious materials | |
| SU1031940A1 (en) | Concrete mix | |
| AT358976B (en) | ADDITIVES FOR INORGANIC BINDERS | |
| AT364640B (en) | BUILDING MATERIAL AND A METHOD FOR THE PRODUCTION THEREOF | |
| SU893939A1 (en) | Concrete mix | |
| SU1655940A1 (en) | Complex additive for concrete mix | |
| JPS5820897B2 (en) | Non-air entraining cement admixture | |
| ITTO940759A1 (en) | MODIFIED MELAMINE RESINS. | |
| JPS6183662A (en) | Cement additive | |
| JPS5913464B2 (en) | Water reducer for mortar and concrete |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |